DE69916218T2 - Long fiber reinforced thermoplastic resin material characterized by the addition of fillers and process for its production - Google Patents

Abstract

Thermoplastic resin material, adapted for injection, compression or extrusion transfer molding, comprises fibres which are ideally arranged in parallel fashion in an impregnation resin; the assembly being sheathed by a thermoplastic matrix resin, in which is incorporated at least a filler, intended to be reinforced by the fibres. An Independent claim is also included for method for making the material.

Description

The The present invention relates to long fiber reinforced thermoplastic Resins and their preparation. These resins are generally used in Shape of bars or ribbons get that afterwards are crushed into granules, and they are used to produce Moldings, in particular by injection molding, hot pressing or transfer extrusion, suitable. The present invention relates to a means to a or more solid fillers in a composition containing such a resin and such Comprising fibers. In order to is to be achieved, the fiber reinforced by the fibers according to the selected Filler type additional To give properties, in particular the rigidity of the material to increase. The introduction of the filler However, it can also have other functions than the mechanical ones To modify properties. As fillers are among others Dyes, antistatic fillers, Stabilizers, etc. to call.

It It is well known to add thermoplastic resins to long fibers strengthen. A common one It was medium, fiber spinning or rovings by extrusion with thermoplastic To coat resins. However, there was a problem in British Patent Specification No. 1,094,439 and partially solved is that resulting from the poor adhesion of certain thermoplastic Resins such as polyolefins on the fibers. This disadvantage was fixed by coating the fibers with the chosen thermoplastic before coating Resin (which can be used as a thermoplastic coating, coating or Matrix resin) with a thermoplastic polymer for wetting (also as a thermoplastic impregnating polymer or resin), such as by grafting with an ethylenically unsaturated polycarboxylic modified polyolefin, impregnated. The impregnation methods However, they were unsatisfactory, with the most realistic in it the fibers were continuous before the final coating through a solution of the impregnating polymer to run. In addition to the risk that traces of solvent in the material stay behind the procedure was not practical and costly because it was a inappropriate treatment with solvent required.

In US Pat. No. 3,993,726 was a continuous one Process for making articles from long glass fibers reinforced described thermoplastic resin. According to the described technique The roving is made with a mixture of thermoplastic wetting resin and to be strengthened thermoplastic resin in an extruder fed Nozzle with Cross spray head impregnated. The impregnation The fibers are made here by placing the fibers of the roving in the Nozzle spreads and these fibers and the thermoplastic blend through a distribution zone (zone d'embarrage) Run around that Material to penetrate well between each fiber. This system was unsatisfactory because the wetting polymer diluted with the other polymer for the most part lost its effectiveness.

• – In einem ersten Schritt werden die Rovings vor ihrem Durchgang durch die Imprägnierdüse ausgebreitet, so daß die einzelnen Fasern des Rovings in etwa nebeneinander liegen. Die Rovings liegen in diesem Fall in Form eines Vlieses oder Bandes vor, die aus einer Folge einzelner paralleler Endlosfasern bestehen. Um beim Ausbreiten des Rovings diese Ausrichtung der Fasern zu erreichen, werden die Rovings in die mit geschmolzenem thermoplastischem Imprägnierharz gespeiste Imprägnierdüse geführt, nachdem sie über wenigstens eine Schikane in der Verteilerzone laufen gelassen wurden, die den Roving aufbricht und so zum Entfalten der Fasern führt, aus denen es besteht. Das so gebildete Vlies oder Band wird dann mit thermoplastischem Imprägnierharz imprägniert und vor der Formdüse durch ein neues Verteilersystem (systeme d'embarrage) gezogen, das aus Schikanen gebildet ist, die zu der ersten oder zu den ersten Schikanen in etwa parallel sind. In diesem System läuft das mit thermoplastischem Imprägnierharz imprägnierte Vlies oder Band durch wenigstens zwei einander gegenüberliegende und zueinander parallele Schikanen. Unter diesen Bedingungen wird der Komplex der mit thermoplastischem Imprägnierharz imprägnierten Fasern in der ersten Schikane auf einer seiner Seiten zerdrückt, wodurch das Harz im geschmolzenen Zustand dazu gebracht wird, zwischen diese Fasern zu dringen und zur gegenüberliegenden Seite zu laufen. Die umgekehrte Wirkung tritt ein, wenn der Komplex der imprägnierten Fasern mit der gegenüberliegenden Schikane in Berührung kommt. Dieses Verteilersystem vor und nach dem Kontakt mit dem thermoplastischen Imprägnierpolymer ermöglicht die individuelle Imprägnierung der Fasern mit einem Minimum an Polymer. Die imprägnierten Fasern laufen schließlich durch eine Formdüse, mit der sich Bänder oder Stäbe herstellen lassen.
• – Am Austrittsende der Formdüse werden die mit thermoplastischem Imprägnierharz imprägnierten Fasern im zweiten Schritt mit dem zu verstärkenden thermoplastischen Harz ummantelt. Hierzu laufen die mit dem thermoplastischen Imprägnierharz imprägnierten Endlosfasern bei einer Temperatur, die vorzugsweise um etwa 40°C über der Schmelztemperatur dieses Imprägnierharzes liegt, durch eine über einen klassischen Querspritzkopf gespeiste Düse, wie sie zum Umhüllen von Draht oder Kabeln verwendet wird. Diese Düse wird mit thermoplastischem Harz gespeist, das mit Fasern verstärkt werden soll, und liegt ungefähr in der Verlängerung der Formdüse des Verteilersystems. Am Austrittsende der Düse werden die Bänder oder Stäbe granuliert. Diese Granalien mit Langfasern, d. h. bei denen die Länge der Fasern der Länge der Granalie entspricht, eignen sich wie oben ausgeführt besonders zum Spritzguß, Warmpressen oder zur Transferextrusion.

Therefore, in order to overcome these drawbacks, the Applicant has developed a method which is the subject of his European patent EP-B-0 342 080 and, thanks to a simple method of maximizing the distribution of the impregnating resin across the fibers of the rovings, uses a minimum impregnation resin to reinforce the largest possible part of the thermoplastic matrix resin. The method consists of passing the rovings through a nozzle fed with a thermoplastic impregnating resin via a crosshead with a first step, after the fibers have been carefully spread. After impregnation of the fibers, the rovings pass in a second step through a second nozzle, which is fed in the same way via a cross-head with the thermoplastic matrix resin, which is compatible with the thermoplastic impregnating resin. According to a particular embodiment, the procedure is as follows:

• - In a first step, the rovings are spread before passing through the impregnating, so that the individual fibers of the roving are approximately side by side. The rovings are in this case in the form of a nonwoven or ribbon, consisting of a series of individual parallel endless fibers. In order to achieve this orientation of the fibers as the roving spreads, the rovings are passed into the impregnating die fed with molten thermoplastic impregnating resin after passing through at least one baffle in the spreading zone which ruptures the roving thus causing the fibers to unfold, which it consists of. The nonwoven or ribbon thus formed is then impregnated with thermoplastic impregnating resin and drawn in front of the die through a new system of distribution (systems d'embarrage) formed from baffles which are approximately parallel to the first or first baffles. In this system, the nonwoven or tape impregnated with thermoplastic impregnating resin passes through at least two opposed and parallel baffles. Under these conditions, the complex of thermoplastic impregnating resin-impregnated fibers in the first baffle is crushed on one side thereof, causing the resin in the molten state to penetrate between these fibers and run to the opposite side. The reverse effect occurs when the complex of impregnated fibers with the opposite chicane comes into contact. This distribution system before and after contact with the thermoplastic impregnating polymer allows the individual impregnation of the fibers with a minimum of polymer. The impregnated fibers finally pass through a die, which can be used to make tapes or rods.
• At the exit end of the die, the impregnated with thermoplastic impregnating resin fibers are coated in the second step with the thermoplastic resin to be reinforced. For this purpose, run through the impregnated with the thermoplastic impregnating resin continuous fibers at a temperature which is preferably about 40 ° C above the melting temperature of this impregnating resin, through a fed via a classic crosshead nozzle, as used for wrapping wire or cables. This nozzle is fed with thermoplastic resin which is to be reinforced with fibers and lies approximately in the extension of the die of the distribution system. At the exit end of the nozzle, the bands or rods are granulated. These granules with long fibers, ie in which the length of the fibers corresponds to the length of the granule are, as stated above, particularly for injection molding, hot pressing or transfer extrusion.

The reinforcement thermoplastic matrix resins such as polypropylene by long fibers allows So, materials with very high rigidity and at the same time very high impact resistance to obtain. The presence of long fibers in the material can however surface defects on the pieces induce the granules of these reinforced thermoplastic resins injection-molded (for example car bumpers). In the best case receives you rob surfaces, where you can guess the presence of the fibers.

at try one or more fixed ones as mentioned above fillers in a composition of long fiber reinforced thermoplastic To bring resins, the Applicant has found that the or the solid fillers not in the impregnating polymer must be introduced. This enabled also to discover that that Introducing at least one solid filler into the thermoplastic matrix resin and thus in the outer part of the bars or ribbons the surface texture the injection-molded pieces improve and make it possible the desired additional To give properties. Because one would like the fibers to be injection molded Products no surface roughness convey more, preferably a larger amount of filler is introduced.

object the present invention is therefore a long fiber reinforced thermoplastic resin material, for the production of molded parts, in particular by injection molding, hot pressing or transfer extrusion, wherein the material is individually in one thermoplastic impregnating resin embedded, approximately parallel endless fibers, wherein the whole of the thermoplastics to be reinforced by these fibers, thermoplastic Called matrix resin, is sheathed, characterized in that at least a filler was incorporated into the thermoplastic matrix resin.

in the In the most general sense, a filler, for the use according to the invention is suitable to be defined as a solid which under the conditions of use does not melt in the context of the present invention and in general no melting point below 400 ° C has.

The filler or at least one of the fillers may be an organic filler, which then consists, for example, of carbon black. Here is a soot with a specific surface area of 50 to 1000 m ² / g to call.

• (a) klassische anorganische Füllstoffe, wie:
• (a1) Wollastonit, kalziniertes oder nicht kalziniertes Kaolin, Talk, Glimmer, gefällte oder ungefällte Kreide, Quarz, Silica, CaSO₄, Dolomit (CaCO₃·MgCO₃), Montmorillonit (Alumosilicat), wobei diese Füllstoffe eine Größe von im allgemeinen zwischen 0,05 μm und 1 mm haben;
• (a2) Glaskügelchen, die einen Durchmesser von im allgemeinen zwischen 0,5 μm und 5 mm haben;
• (a3) Glas- oder Kohlefasern, die eine Länge von im allgemeinen zwischen 100 μm und 20 mm und einen Durchmesser von im allgemeinen zwischen 0,5 μm und 1 mm haben;
• (b) flammhemmende Füllstoffe, wie Al(OH)₃, Mg(OH)₂, Huntit (3MgCO₃·CaCO₃), Hydromagnesit (3MgCO₃·Mg(OH)₂·3H₂O), Sb₂O₃, Sb₂O₅, Ammoniumpolyphosphat und Melaminpolyphosphat, wobei diese Füllstoffe eine Größe von im allgemeinen zwischen 0,05 μm und 1 mm haben;
• (c) Füllstoffe mit hoher Dichte, wie BaSO₄, ZrSiO₄, Fe₃O₄, wobei diese Füllstoffe eine Größe von im allgemeinen zwischen 0,05 μm und 1 mm haben;
• (d) leitfähige Füllstoffe, wie:
• (d1) Metallfasern, wie Aluminium-, Kupfer-, Eisen-, Edelstahlfasern, wobei diese Fasern eine Länge von im allgemeinen zwischen 100 μm und 20 mm und einen Durchmesser von im allgemeinen zwischen 0,5 μm und 1 mm haben;
• (d2) mit Metallen wie Nickel überzogene Glasfasern, wobei diese Fasern eine Länge von im allgemeinen zwischen 100 μm und 20 mm und einen Durchmesser von im allgemeinen zwischen 0,5 μm und 1 mm haben;
• (d3) Metallteilchen, wie Aluminiumflakes, mit einer Dimension von im allgemeinen 0,1 bis 10 mm² × 5 μm bis 1 mm Dicke; und
• (d4) metallisierte Teilchen, wie mit Nickel überzogener Glimmer oder mit Silber überzogene Glaskügelchen.

The filler or at least one of the fillers may also be an inorganic filler, in particular an inorganic filler having a specific surface area below 50 m ² / g and more generally below 20 m ² / g. Examples of inorganic fillers are:

• (a) classical inorganic fillers, such as:
• (a1) wollastonite, calcined or uncalcined kaolin, talc, mica, precipitated or precipitated chalk, quartz, silica, CaSO ₄ , dolomite (CaCO ₃ .MgCO ₃ ), montmorillonite (aluminosilicate), these fillers having a size generally between 0.05 μm and 1 mm;
• (a2) glass beads having a diameter of generally between 0.5 μm and 5 mm;
• (a3) glass or carbon fibers having a length of generally between 100 μm and 20 mm and a diameter of generally between 0.5 μm and 1 mm;
• (b) Flame retardant fillers such as Al (OH) ₃ , Mg (OH) ₂ , Huntite (3MgCO ₃ .CaCO ₃ ), Hydromagnesite (3MgCO ₃ .Mg (OH) ₂ .3H ₂ O), Sb ₂ O ₃ , Sb ₂ O ₅ , ammonium polyphosphate and melamine polyphosphate, said fillers having a size of generally between 0.05 μm and 1 mm;
• (c) high density fillers such as BaSO ₄ , ZrSiO ₄ , Fe ₃ O ₄ , these fillers being of a size generally mine between 0.05 μm and 1 mm;
• (d) conductive fillers, such as:
• (d1) metal fibers, such as aluminum, copper, iron, stainless steel fibers, these fibers having a length of generally between 100 μm and 20 mm and a diameter of generally between 0.5 μm and 1 mm;
• (d2) glass fibers coated with metals such as nickel, these fibers having a length of generally between 100 μm and 20 mm and a diameter of generally between 0.5 μm and 1 mm;
• (d3) metal particles, such as aluminum flakes, having a dimension of generally 0.1 to 10 mm ² × 5 μm to 1 mm in thickness; and
• (d4) metallized particles, such as nickel-coated mica or silver-coated glass beads.

A special family of inorganic fillers is that of the particulate inorganic fillers, which has a mean particle size diameter from 20 nm to 500 μm, in particular from 50 nm to 100 μm to have.

Further may be one or at least one filler be used, the surface-treated has been. Indeed can the fillers surface treated with the target have been to improve their dispersion within the matrix or the viscosity this filled Polymer or to reduce the mechanical properties of the filled Modify polymer. As usual surface treatment is the treatment with fatty acids (for example stearic acid), To name silanes, titanates, etc.

The Introducing the filler (s) Further, according to the nature of the filler, various functions have: for coloring, as antistatic, as stabilizer, for the modification of the mechanical Properties. The choice of one or more fillers, one or the other To obtain special property is within the skill of the artisan. So can the soot in greater Amount (for example, more than 10 wt .-%, even more than 20 wt .-%, based on the total weight of impregnating and matrix resin + long fibers + Filler (s)) serve, conductivity to mediate and therefore confer antistatic properties.

As made clear above, can be a filler or a mixture be used from organic and / or inorganic fillers. So can the filler Soot and an inorganic filler include no carbon. On the other hand, the filler be readily free of carbon and must therefore no soot a.

It So there is no lower limit on what the amount of filler (s) relates, which are to be incorporated into the matrix resin. So can the filler (s), for example as a dye, less than 1 wt .-% introduced, based on the total weight of impregnating and matrix resin + Long fibers + fillers; as an example carbon black may be mentioned become.

Yet lie the filler or fillers advantageous in an amount sufficient to reduce the roughness of the surface of the pieces formed from this granulate as a result of the long reinforcing fibers to eliminate. For this purpose, a filler amount of more than 1 % By weight, for example at least 2% by weight, in particular 2 to 30 wt .-%, based on the total weight impregnating and Matrix resin + long fibers + filler (s).

• (A) 10 bis 50 Gew.-%, insbesondere 20 bis 40 Gew.-% Langfasern; und
• (B) 5 bis 40 Gew.-%, insbesondere 10 bis 20 Gew.-% thermoplastisches Imprägnierharz;
• (C) 20 bis 88 Gew.-%, insbesondere 40 bis 70 Gew.-% Matrixharz (ohne den oder die Füllstoffe);
• (D) bis zu 30 Gew.-%, insbesondere 2 bis 30 Gew.-% des oder der Füllstoffe,

wobei das Matrixharz ferner wenigstens einen üblichen Zusatzstoff wie einen Farbstoff oder einen Stabilisator enthalten kann.The materials according to the invention may have the following composition per 100% by weight of (A) + (B) + (C) + (D):

• (A) 10 to 50 wt .-%, in particular 20 to 40 wt .-% long fibers; and
• (B) 5 to 40 wt .-%, in particular 10 to 20 wt .-% thermoplastic impregnating resin;
• (C) 20 to 88% by weight, in particular 40 to 70% by weight of matrix resin (without the filler or fillers);
• (D) up to 30% by weight, in particular from 2 to 30% by weight, of the filler (s),

wherein the matrix resin may further contain at least one conventional additive such as a dye or a stabilizer.

The Continuous fibers for reinforcement serve the thermoplastic resins are known. They are organic or inorganic. As an example Rovings made of glass, silicon, carbon or aramid fibers called become.

• – gepfropftes Polyethylen hoher Dichte – Polyethylen niederer Dichte;
• – gepfropftes Polyethylen hoher Dichte – Ethylen-Vinylacetat-Copolymer (EVA);
• – gepfropftes EVA – Polyvinylchlorid;
• – gepfropftes Polypropylen – Polypropylen;
• – sequenziertes Polyetheramid-Copolymer – Polyamid;
• – funktionalisiertes Polyamid (beispielsweise α,ω-Diamine, α,ω-Disäuren, α-Amin-ω-Säure, Monoamin) – Polyamid;
• – modifiziertes EVA – EVA oder Polyethylen niederer Dichte (LDPE);
• – gepfropftes lineares Polyethylen niederer Dichte (LLDPE) – LLDPE oder LDPE,

kompatibel, während ein Vinylchlorid-Homopolymer und ein Styrol-Homopolymer inkompatibel sind.As has already been explained in more detail, the thermoplastic impregnating polymer must be mixed with the ether compatible with thermoplastic matrix polymer. This compatibility, while well known to those skilled in the art and of considerable practical importance, is a property that has never, truly, satisfactorily been defined scientifically. Without going into the highly controversial details of partial reciprocal miscibility of the polymers in question, it is here assumed that two polymers are compatible if it is possible to mix them to give a material exhibiting a mechanical behavior similar to that of the present invention or better than that of the worse of the two. For example, according to this definition, the pairs are:

• Grafted high density polyethylene - low density polyethylene;
• Grafted high density polyethylene - ethylene vinyl acetate copolymer (EVA);
• - grafted EVA - polyvinyl chloride;
• - grafted polypropylene - polypropylene;
• Sequenced polyetheramide copolymer - polyamide;
• Functionalized polyamide (for example α, ω-diamines, α, ω-diacids, α-amino-ω-acid, monoamine) - polyamide;
• Modified EVA EVA or low density polyethylene (LDPE);
• Grafted linear low density polyethylene (LLDPE) - LLDPE or LDPE,

compatible, while a vinyl chloride homopolymer and a styrene homopolymer are incompatible.

Under thermoplastic impregnating polymer is understood to mean a polymer that makes it possible to apply the surface to one intimate contact of fiber polymer to enlarge, so it is the role plays a coupling agent. The role of coupling agents becomes in Polymer Engineering Composite, M.O.W. Richardson - Appl. Sc. Publ. 1977, where the organosilanes are the best known are.

The thermoplastic impregnating polymer becomes ordinary selected from polymers with a low viscosity or also among polymers, their polarity across from the corresponding original polymer is increased.

The Low viscosity polymer is preferably a polymer whose melt viscosity (Θf + 40 ° C) is at most equal to that of a polypropylene having a melt index of 20 (Melt Index) at 230 ° C less than 2,16 kg according to the norm ASTM D 1328 is.

Under The polymers with low viscosity can be called: by Peroxidabbau modified polymers as in the case of, for example, polypropylene, Polyamide, polystyrene, or even polymers resulting from the polyaddition a functionalized polyamide oligomer with a co-reactant such as For example, a polyepoxide or a polyisocyanate or a functionalized polypropylene oligomer with a co-reactant such as for example a polyether diol, dihydroxypolybutadiene or an α, ω-diamine polyamide result. These low viscosity polymers will be also from saturated Polyesters such as polybutylene terephthalate (PBT) or polyethylene terephthalate (PET) whose chains are cut by controlled decomposition, that he receives a functional oligomer. This formation of functional oligomer can be achieved by kneading the saturated Polyester in the heat in the presence of diamine and in particular Reach dodecanediamine.

Under the polymers, their polarity across from the corresponding original polymer is increased, the polymers preferably, which optionally have reactive polar centers. The polymers having polar centers are generally polymers, either by grafting or by sequencing with, for example maleic anhydride, Acrylic acid, Vinyl acetate in the case of polyethylene, polypropylene or the copolymers or more generally with compounds that are, for example, polar Centers of the type of a ketone, an aldehyde, an acid, one Esters, cyan, amine, etc., are modified.

• – gepfropftes Polypropylen, wie mit Maleinsäureanhydrid oder Acrylsäure gepfropftes Polypropylen;
• – Polyethylenvinylacetat als solches oder gepfropft mit Maleinsäureanhydrid;
• – gepfropftes Polyethylen hoher Dichte, wie mit Acrylsäure oder Maleinsäureanhydrid gepfropftes Polyethylen hoher Dichte;
• – gepfropftes lineares Polyethylen niederer Dichte, wie mit Acrylsäure oder Maleinsäureanhydrid gepfropftes lineares Polyethylen niederer Dichte;
• – sequenzierte Polyetheramid-Copolymere.

Among the grafted or sequenced modified, especially recommended polymers are:

• Grafted polypropylene, such as polypropylene grafted with maleic anhydride or acrylic acid;
• - Polyethylene vinyl acetate as such or grafted with maleic anhydride;
• Grafted high density polyethylene, such as high density polyethylene grafted with acrylic acid or maleic anhydride;
• Grafted linear low density polyethylene such as linear low density polyethylene grafted with acrylic acid or maleic anhydride;
• - Sequenced polyetheramide copolymers.

Certain Imprägnierpolymere can directly by grafting or controlled degradation in situ at the step the impregnation the rovings are made. For this purpose, the ingredients are polymer, Decomposing agent and optionally grafting agent in the molten state in the extruder that feeds the impregnation nozzle, react. In the case of degradation by peroxide, one chooses from the peroxides, preferably those which, at the reaction temperature, usually between 180 and 250 ° C is a half-life of less than or equal to the residence time of the polymer in the extruder. The proportion of the grafting agent and / or decomposition agent is generally between 0.5 and 3 wt .-% based on the weight of the base polymer.

To call is the use of impregnating and matrix resins, the both of which comprise a propylene polymer. Under propylene polymer understands optionally, a polymer comprising polymerized propylene units with one or more comonomers, such as ethylene.

Especially to mention is the use as impregnating resin, one with 0.5-1.5 wt .-% maleic anhydride (for example, 1% by weight) of maleated polypropylene having a MFI ("Melt Flow Index ", melt index) from 1 to 1000 (eg 400) measured at 230 ° C below 2.16 kg, or a mixture of such a polypropylene with a Polypropylene homopolymer having an MFI of 1 to 1000 (for example 40), measured at 230 ° C below 2.16 kg, and at the same time, as a matrix resin, of a polypropylene with an MFI of 1 to 100 (for example 40) measured at 230 ° C under 2.16 kg, optionally with a small amount of a 0.5-1.5 wt .-% maleic anhydride maleinized polypropylene having an MFI of 1 to 1000 (e.g. 400), measured at 230 ° C below 2.16 kg.

in the Case of a halogenated thermoplastic matrix resin into which a solid filler is incorporated, the impregnating resin not be based on or contain alkyl (meth) acrylate.

object The present invention further provides a method of preparation one reinforced by long fibers thermoplastic resin material as defined above, wherein the process being characterized in that it consists in the long fibers, in the form of rovings, by extrusion with a thermoplastic impregnating in an over To impregnate a nozzle fed with a crosshead, wherein the impregnated Rovings afterwards at a temperature above the melting temperature of the thermoplastic impregnating again in a second nozzle where they are mixed with the thermoplastic matrix resin, in the at least one filler was incorporated, to be jacketed.

According to one special feature of this process are the rovings in front of the impregnation of the rovings with the thermoplastic impregnating resin by passage through spread a distribution zone and after impregnation the rovings will be pulled into a second distribution zone, before they are formed and run through the second nozzle to the shell.

The with the impregnating resin impregnated Endless fibers emerge from the die, with the impregnating resin is in molten state. They preferably cool in contact with the room air before entering the second nozzle with matrix resin is fed, in which at least one filler was incorporated. Before entering this nozzle are those with the impregnating resin impregnated Continuous fibers generally at a temperature between 40 and 80 ° C.

Of the Distance between the die for the with thermoplastic impregnating resin impregnated continuous fibers and the nozzle depends on the jacket from the thermal properties of the resin used. This Distance depends also on the drawing speed of the extruded material. This distance should preferably be as low as possible and is in the Practice usually 0.1 to 4 meters.

The mass ratios of impregnating polymer to matrix standard polymer from the ultimately desired mass fractions fiber.

According to one particular embodiment the method according to the invention you leave the Rovings in a first step through a distribution zone, to spread it, let it one Go through the impregnation nozzle, by means of an extruder with thermoplastic impregnating resin is fed, which impregnated Rovings pass through a second distribution zone and they pass through a shaping nozzle, and in a second step go through with thermoplastic impregnating impregnated Rovings a nozzle for wrapping, the approximately in the extension the tool of the first step is that of a second extruder with is fed to the thermoplastic matrix resin, in the at least one filler was incorporated.

What the incorporation of the filler (s) in the thermoplastic matrix resin, so can be before extrusion by Knead a premix of thermoplastic matrix resin and the or make the fillers, for example, using a Buss co-kneader, or the or the fillers can also be fed directly to the extruder, which feeds the nozzle for wrapping.

The just described method provides bands or rods that be crushed into granules. The granules generally have a length from 3 mm to 100 mm.

A detailed Description of the two steps of the method according to the invention was in the introductory Part of the present description with reference to EP-B-0 342,080 given.

• – Die Prozentangaben beziehen sich auf das Gewicht, sofern nicht anders angegeben;
• – die Werte für den Schmelzindex (Melt Index) wurden entsprechend ISO-Norm 1133 : 91 bei 230°C unter 2,16 kg gemessen;
• – Die Dreipunkt-Biegetests (ISO-Norm 178) und die Stoßfestigkeitstests nach Charpy (ISO-Norm 179) wurden an Teststücken von 80 × 10 × 4 mm³ durchgeführt, die aus spritzgeformten Platten parallel zum Spritzguß ausgestanzt wurden;
• – die Oberflächenbeschaffenheit wurde an Hand des in der französischen Automobilindustrie verwendeten Profilkriteriums Ra gemäß der Norm E 05 015 bewertet, wobei Ra der mittleren Abweichung des Profils entspricht.

The following examples illustrate the present invention without, however, limiting its scope. In these examples:

• - The percentages are by weight unless otherwise stated;
• - the Melt Index values were measured according to ISO standard 1133: 91 at 230 ° C under 2.16 kg;
• - The three-point bending tests (ISO standard 178) and the Charpy impact tests (ISO standard 179) were carried out on test pieces of 80 × 10 × 4 mm ³ punched out of injection-molded plates parallel to the injection molding;
• - the surface finish was evaluated on the basis of the profile criterion Ra used in the French automotive industry in accordance with standard E 05 015, where Ra corresponds to the mean deviation of the profile.

• – Zone 1 Verteilerzone:
• – Länge: 70 mm
• – Breite: 145 mm
• – Spalt: 5 mm
• – konisch aufgeweitetes Eintrittsende und eine kegelförmige Schikane mit 10 mm Höhe
• – Zone 2 der Imprägnierdüse
• – Länge: 125 mm
• – Breite: 100 mm
• – sechs Speisekanäle mit rechtwinkligem Querschnitt von 20 × 5 mm
• – Spalt am Austrittsende der Zone: 5 mm
• – Zone 3 Verteilerzone
• – Länge: 200 mm
• – Breite: 100 mm
• – sinusförmiger Verteiler mit 7 Scheitelpunkten
• – Amplitude zwischen Scheitelpunkten: 25 mm
• – Spalt: 3 mm
• – Zone 3a zum Tränken (identisch mit Zone 4)
• – Länge: 500 mm
• – Breite: 145 mm
• – Zone 4 zur Formung
• – Düse mit sechs Öffnungen mit 1,8 bis 2 mm Durchmesser
• – Länge: 175 mm
• – Breite: 100 mm

The used impregnation nozzle is of the same type as the 1 FR-2 630 967 and comprises the following zones:

• - Zone 1 distribution zone:
• - Length: 70 mm
• - Width: 145 mm
• - gap: 5 mm
• - conically widened entrance end and a conical chicane with 10 mm height
• - Zone 2 of the impregnation nozzle
• - Length: 125 mm
• - Width: 100 mm
• - six feed channels with a rectangular cross-section of 20 × 5 mm
• - gap at the outlet end of the zone: 5 mm
• - Zone 3 distribution zone
• - Length: 200 mm
• - Width: 100 mm
• - sinusoidal distributor with 7 vertices
• - Amplitude between vertices: 25 mm
• - gap: 3 mm
• - Zone 3a for watering (identical to zone 4)
• - Length: 500 mm
• - Width: 145 mm
• - Zone 4 for shaping
• - Nozzle with six openings of 1.8 to 2 mm diameter
• - Length: 175 mm
• - Width: 100 mm

EXAMPLE 1

The impregnation The glass fibers in a first step in an impregnating, the fed at right angles through a single screw extruder. This extruder is itself fed with polypropylene, which with 1 maleic anhydride is maleinated and has a melt index (melt index) of about 400 Has. It is kept at an average temperature of 200 ° C.

In at 320 ° C Be kept impregnation nozzle six glass rovings E 2400 tex run. At a speed of 22.2 meters / minute become bars, their mass fraction of glass is about 70%, through openings with 1.8 mm diameter drawn.

• – 60% Polypropylen-Homopolymer mit einem Schmelzindex von etwa 40;
• – 20% Glimmer; und
• – 20% ganze Glaskügelchen.

These rods then pass through a jacketing nozzle located 20 cm from the first one. This second nozzle, which lies approximately in the extension of the first, is maintained at a temperature of 270 ° C. It is mounted at right angles to a single screw extruder maintained at an average temperature of 280 ° C and charged with the following mixture previously prepared with a Buss co-kneader:

• - 60% polypropylene homopolymer with a melt index of about 40;
• - 20% mica; and
• - 20% whole glass beads.

From the 5.4 mm openings this nozzle become bars drawn with a glass mass fraction of about 20%, which is then cooled and to a length granulated by 15 mm.

The mechanical properties and the surface texture of the injection molded Products are given in Table 1.

EXAMPLE 2 (comparative)

example 1 is repeated, except that the extruder is at right angles to the jacket nozzle with a polypropylene homopolymer is charged, which has a melt index of about 40.

The mechanical properties and the surface texture of the injection molded Products are given in Table 1. You also put quality a less good surface finish the granules injection molded plates than in the case of example 1.

EXAMPLE 3

• – 77% Polypropylen-Homopolymer mit einem Schmelzindex von etwa 40, und
• – 23% Polypropylen, das mit 1% Maleinsäureanhydrid maleinisiert ist, mit einem Schmelzindex von etwa 400.

The impregnation of the glass fibers is carried out in a first step in an impregnating, which is fed at right angles by a single-screw extruder. This extruder is itself charged with a mixture of:

• - 77% polypropylene homopolymer with a melt index of about 40, and
• - 23% polypropylene maleinated with 1% maleic anhydride, having a melt index of about 400.

Of the Extruder is maintained at an average temperature of 220 ° C.

By at 400 ° C Be kept impregnation nozzle twelve glass rovings E 1200 tex run, the previously with the help of ceramic bands in pairs were connected. At a speed of 20 meters / minute become bars, their mass fraction of glass is about 60%, through openings with 2 mm diameter drawn.

• – 89% Polypropylen-Homopolymer mit einem Schmelzindex von etwa 40;
• – 1,5% Polypropylen, das mit 1% Maleinsäureanhydrid maleinisiert ist, mit einem Schmelzindex von etwa 400;
• – 8% Wollastonit; und
• – 1,5% Talk.

These rods then pass through a jacketing nozzle located 20 cm from the first one. This second nozzle, which lies approximately in the extension of the first, is maintained at a temperature of 250 ° C. It is mounted at right angles to a single-screw extruder maintained at an average temperature of 220 ° C and charged with the following mixture previously prepared with a Buss co-kneader:

• - 89% polypropylene homopolymer with a melt index of about 40;
• 1.5% polypropylene maleinated with 1% maleic anhydride, having a melt index of about 400;
• - 8% wollastonite; and
• - 1.5% talc.

The mechanical properties and the surface texture of the injection molded Products are given in Table 1.

EXAMPLE 4 (comparative)

example 3 is repeated, except that the extruder is at right angles to the jacket nozzle with a polypropylene homopolymer is charged, which has a melt index of about 40.

The mechanical properties and surface finish of the injection molded product are given in Table 1.

Claims (27)

A long fiber reinforced thermoplastic resin material suitable for use in the manufacture of moldings, in particular by injection molding, hot pressing or transfer extrusion, said material individually comprising approximately parallel continuous filaments embedded in a thermoplastic impregnating resin, the whole being comprised of the thermoplastics to be reinforced by said fibers , called thermoplastic matrix resin, is coated, characterized in that at least one filler has been incorporated into the thermoplastic matrix resin. Material according to claim 1, characterized that the filler or at least one of the fillers an organic filler is. Material according to claim 2, characterized that the organic filler consists of carbon black. Material according to claim 3, characterized in that the carbon black is a carbon black having a specific surface area of 50 to 1000 m ² / g. Material according to claim 1, characterized that the filler or at least one of the fillers an inorganic filler is. Material according to claim 5, characterized in that an inorganic filler has a specific surface area below 50 m ² / g and more generally below 20 m ² / g. Material according to either of Claims 5 and 6, characterized in that the inorganic filler or fillers are selected from: (a) conventional inorganic fillers, such as: (a1) wollastonite, calcined or non-calcined kaolin, talc, mica, precipitated or unfolded chalk , Quartz, silica, CaSO ₄ , dolomite (CaCO ₃ .MgCO ₃ ), montmorillonite (aluminosilicate), these fillers having a size of generally between 0.05 μm and 1 mm; (a2) glass beads having a diameter of generally between 0.5 μm and 5 mm; (a3) glass or carbon fibers having a length of generally between 100 μm and 20 mm and a diameter of generally between 0.5 μm and 1 mm; (b) flame retardant fillers such as Al (OH) ₃ , Mg (OH) ₂ , Huntite (3MgCO ₃ .CaCO ₃ ), Hydromagnesite (3MgCO ₃ .Mg (OH) ₂ .3H ₂ O), Sb ₂ O ₃ , Sb ₂ O ₅ , ammonium polyphosphate and melamine polyphosphate, said fillers having a size of generally between 0.05 μm and 1 mm; (c) high density fillers such as BaSO ₄ , ZrSiO ₄ , Fe ₃ O ₄ , these fillers having a size generally between 0.05 μm and 1 mm; (d) conductive fillers such as: (d1) metal fibers, such as aluminum, copper, iron, stainless steel fibers, which fibers are generally between 100 μm and 20 mm in length and generally between 0.5 μm in diameter and 1 mm; (d2) glass fibers coated with metals, such as nickel, which fibers have a length of generally between 100 μm and 20 mm and a diameter of generally between 0.5 μm and 1 mm; (d3) metal particles, such as aluminum flakes, having a dimension of generally 0.1 to 10 mm ² × 5 μm to 1 mm in thickness; and (d4) metallized particles, such as nickel-coated mica or silver-coated glass beads. Material according to one of claims 5 or 6, characterized that the or the inorganic fillers particulate fillers are those that have a mean particle size diameter of 20 nm up to 500 microns, in particular from 50 nm to 100 μm to have. Material according to one of claims 1 to 8, characterized that the filler or at least one filler surface treated has been. Material according to one of claims 1 to 9, characterized that the filler or the fillers are present in sufficient quantity to the surface roughness of the moldings this material, surface roughness as a result of long fibers for reinforcement, eliminate. Material according to one of claims 1 to 10, characterized that the or the fillers more than 1% by weight of the total weight of impregnating and matrix resin + long fibers + Filler (s) turn off. Material according to claim 10, characterized that the or the fillers at least 2% by weight of the total weight of impregnating and matrix resin + long fibers + Filler (s) turn off. Material according to claim 12, characterized that the or the fillers 2 to 30 wt .-% of the total weight of impregnating and matrix resin + long fibers + Filler (s) turn off. Material according to one of claims 1 to 13, characterized that it the following composition per 100% by weight of (A) + (B) + (C) + (D) has: (A) 10 to 50% by weight of long fibers; and (B) 5 to 40% by weight of thermoplastic impregnating resin; (C) 20 to 88% by weight of matrix resin (without the filler or fillers); (D) up to 30% by weight of the filler (s), in which the matrix resin at least one usual Additive such as a dye or a stabilizer can. Material according to one of claims 1 to 14, characterized that it does not include soot. Material according to one of claims 1 to 15, characterized that the Long fibers glass, quartz, coal or Aramid fibers are. Material according to one of claims 1 to 16, characterized that this impregnating and the matrix resin all comprise a propylene polymer. Material according to one of claims 1 to 17, characterized that this impregnating a maleinated with 0.5 to 1.5 weight percent maleic anhydride Polypropylene with an MFI of 1 to 1000, measured at 230 ° C under 2.16 kg, or a mixture of such a polypropylene with a Polypropylene homopolymer having an MFI of 1 to 1000, measured at 230 ° C below 2.16 kg, and the matrix resin is a polypropylene with an MFI from 1 to 100, measured at 230 ° C below 2.16 kg, optionally with a small amount of one with from 0.5 to 1.5% by weight of maleic anhydride maleinized polypropylene having an MFI of 1 to 1000 at 230 ° C below 2.16 kg. Material according to one of claims 1 to 18, characterized that this impregnating in the case of a halogenated thermoplastic matrix resin, the a solid filler incorporated, no polymer based on alkyl (meth) acrylate is or includes such. Granules obtained by crushing rods or bands as claimed in any one of the claims 1 to 19 defined material. Method for producing a long fiber increased thermoplastic resin material as claimed in any of claims 1 to 19, characterized in that it consists in the long fibers, in Shape of rovings, by extrusion with a thermoplastic impregnating resin in an over To impregnate a nozzle fed with a crosshead, wherein the impregnated Rovings afterwards at a temperature above the melting temperature of the thermoplastic impregnating taken up again in a second nozzle where they are with the thermoplastic matrix resin, in the at least a filler was incorporated, to be jacketed. Method according to claim 21, characterized that the Rovings before impregnation of the rovings with the thermoplastic impregnating resin by passage through a distribution zone are spread, and in that the rovings after impregnation are pulled into a second distribution zone before they are formed and through the second nozzle to the jacket run. Method according to one of claims 21 or 22, characterized that the with thermoplastic impregnating resin impregnated Rovings from the first nozzle emerge, with the resin in a molten state, and into the second nozzle at a temperature between 40 and 80 ° C. A process according to any one of claims 21 to 23, characterized in that the rovings are passed through a distribution zone in a first step to spread them through an impregnating die fed by an extruder with thermoplastic impregnating resin run impregnated rovings through a second distribution zone and that they pass through a molding die, and there in that, in a second step, the thermoplastic impregnating resin impregnated rovings pass through a jacket nozzle approximately in the extension of the first step tool fed by a second thermoplastic matrix resin extruder into which at least one filler has been incorporated , Method according to one of Claims 21 to 24, characterized that he by kneading before extrusion, a premix of the thermoplastic Matrix resin and the filler or fillers generated. Method according to one of claims 21 to 25, characterized that he the filler (s) directly onto the extruder, which feeds the nozzle to the casing. Method according to one of claims 21 to 26, characterized that it Bars or Supplies ribbons, which is crushed to form granules.